Publications

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We present the results of a three year LDRD project that focused on understanding the impact of defects on the electrical, optical and thermal properties of GaN-based nanowires (NWs). We describe the development and application of a host of experimental techniques to quantify and understand the physics of defects and thermal transport in GaN NWs. We also present the development of analytical models and computational studies of thermal conductivity in GaN NWs. Finally, we present an atomistic model for GaN NW electrical breakdown supported with experimental evidence. GaN-based nanowires are attractive for applications requiring compact, high-current density devices such as ultraviolet laser arrays. Understanding GaN nanowire failure at high-current density is crucial to developing nanowire (NW) devices. Nanowire device failure is likely more complex than thin film due to the prominence of surface effects and enhanced interaction among point defects. Understanding the impact of surfaces and point defects on nanowire thermal and electrical transport is the first step toward rational control and mitigation of device failure mechanisms. However, investigating defects in GaN NWs is extremely challenging because conventional defect spectroscopy techniques are unsuitable for wide-bandgap nanostructures. To understand NW breakdown, the influence of pre-existing and emergent defects during high current stress on NW properties will be investigated. Acute sensitivity of NW thermal conductivity to point-defect density is expected due to the lack of threading dislocation (TD) gettering sites, and enhanced phonon-surface scattering further inhibits thermal transport. Excess defect creation during Joule heating could further degrade thermal conductivity, producing a viscous cycle culminating in catastrophic breakdown. To investigate these issues, a unique combination of electron microscopy, scanning luminescence and photoconductivity implemented at the nanoscale will be used in concert with sophisticated molecular-dynamics calculations of surface and defect-mediated NW thermal transport. This proposal seeks to elucidate long standing material science questions for GaN while addressing issues critical to realizing reliable GaN NW devices.

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Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

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Active cooling of electronic systems for space-based and terrestrial National Security missions has demanded use of Stirling, reverse-Brayton, closed Joule-Thompson, pulse tube and more elaborate refrigeration cycles. Such cryocoolers are large systems that are expensive, demand large powers, often contain moving parts and are difficult to integrate with electronic systems. On-chip, solid-state, active cooling would greatly enhance the capabilities of future systems by reducing the size, cost and inefficiencies compared to existing solutions. We proposed to develop the technology for a thermoelectric cooler capable of reaching 77K by replacing bulk thermoelectric materials with arrays of Bi{sub 1-x}Sb{sub x} nanowires. Furthermore, the Sandia-developed technique we will use to produce the oriented nanowires occurs at room temperature and can be applied directly to a silicon substrate. Key obstacles include (1) optimizing the Bi{sub 1-x}Sb{sub x} alloy composition for thermoelectric properties; (2) increasing wire aspect ratios to 3000:1; and (3) increasing the array density to {ge} 10{sup 9} wires/cm{sup 2}. The primary objective of this LDRD was to fabricate and test the thermoelectric properties of arrays of Bi{sub 1-x}Sb{sub x} nanowires. With this proof-of-concept data under our belts we are positioned to engage National Security systems customers to invest in the integration of on-chip thermoelectric coolers for future missions.

Carbon nanotubes have shown promise for applications in many diverse areas of technology. In this report we describe our efforts to develop high-current cathodes from a variety of nanotubes deposited under a variety of conditions. Our goal was to develop a one-inch-diameter cathode capable of emitting 10 amperes of electron current for one second with an applied potential of 50 kV. This combination of current and pulse duration significantly exceeds previously reported nanotube-cathode performance. This project was planned for two years duration. In the first year, we tested the electron-emission characteristics of nanotube arrays fabricated under a variety of conditions. In the second year, we planned to select the best processing conditions, to fabricate larger cathode samples, and to test them on a high-power relativistic electron beam generator. In the first year, much effort was made to control nanotube arrays in terms of nanotube diameter and average spacing apart. When the project began, we believed that nanotubes approximately 10 nm in diameter would yield sufficient electron emission properties, based on the work of others in the field. Therefore, much of our focus was placed on measured field emission from such nanotubes grown on a variety of metallized surfaces and with varying average spacing between individual nanotubes. We easily reproduced the field emission properties typically measured by others from multi-wall carbon nanotube arrays. Interestingly, we did this without having the helpful vertical alignment to enhance emission; our nanotubes were randomly oriented. The good emission was most likely possible due to the improved crystallinity, and therefore, electrical conductivity, of our nanotubes compared to those in the literature. However, toward the end of the project, we learned that while these 10-nm-diameter CNTs had superior crystalline structure to the work of others studying field emission from multi-wall CNT arrays, these nanotubes still had a thin coating of glassy carbon surrounding them in a sheath-like manner. This glassy carbon, or nano-crystalline graphite, is likely to be a poor conductor due to phonon scattering, and should actually be deleterious for extracting electrons with electric fields. While we did not achieve the field emission reported for single-wall carbon nanotubes that spurred the idea for this project, at the year's very end, we had a breakthrough in materials growth and learned to control the growth of very-small diameter nanotubes ranging from 1.4 to 7 nm. The 1.4-nm nanotubes are single-walled and grow at only 530 C. This is the lowest temperature known to result in single-wall carbon nanotubes, and may be very important for many applications that where certain substrates could not be used due to the high temperatures commonly used for CNT growth. Critically important for field emission, these small diameter nanotubes, consisting of only a few concentric graphene cylindrical walls, do not show the presence of a poorly-conductive sheath material. Therefore, these nanotubes will almost definitely have superior field emission properties to those we already measured, and it is possible that they could provide the necessary field emission to make this project successful. Controlled spacing and lengths of these single-wall nanotubes have yet to be explored, along with correlating their structures to their improved field emission. Unfortunately, we did not discover the methods to grow these highly-crystalline and small diameter CNTs until late in the year. Since we did not achieve the necessary emission properties by mid-year, the project was ''prematurely'' terminated prior to the start of the second year. However, it should be noted that with the late developments, this work has not hit the proverbial ''brick wall''. Clearly the potential still exists to reproduce and even exceed the high emission results reported for randomly-oriented and curly single-wall carbon nanotubes, both in terms of total field emitting currents and perhaps more importantly, in reproducibility.

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We have built and tested a miniaturized, thermoelectric power source that can provide in excess of 450 {micro}W of power in a system size of 4.3cc, for a power density of 107 {micro}W/cc, which is denser than any system of this size previously reported. The system operates on 150mW of thermal input, which for this system was simulated with a resistive heater, but in application would be provided by a 0.4g source of {sup 238}Pu located at the center of the device. Output power from this device, while optimized for efficiency, was not optimized for form of the power output, and so the maximum power was delivered at only 41mV. An upconverter to 2.7V was developed concurrently with the power source to bring the voltage up to a usable level for microelectronics.

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Multiwall carbon nanotubes are grown via thermal chemical vapor deposition between temperatures of 630 and 830 C using acetylene in nitrogen as the carbon source. This process is modeled using classical thermodynamics to explain the total carbon deposition as a function of time and temperature. An activation energy of 1.60 eV is inferred for nanotube growth after considering the carbon solubility term. Scanning electron microscopy shows growth with diameters increasing linearly with time. Transmission electron microscopy and Raman spectroscopy show multiwall nanotubes surrounded by a glassy-carbon sheath, which grows with increasing wall thickness as growth temperatures and times rise.

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A variety of solution deposition routes have been reported for processing complex perovskite-based materials such as ferroelectric oxides and conductive electrode oxides, due to ease of incorporating multiple elements, control of chemical stoichiometry, and feasibility for large area deposition. Here, we report an extension of these methods toward long length, epitaxial film solution deposition routes to enable biaxially oriented YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (YBCO)-coated conductors for superconducting transmission wires. Recent results are presented detailing an all-solution deposition approach to YBCO-coated conductors with critical current densities J{sub c} (77 K) > 1 MA/cm{sup 2} on rolling-assisted, biaxially textured, (200)-oriented Ni-W alloy tapes. Solution-deposition methods such as this approach and those of other research groups appear to have promise to compete with vapor phase methods for superconductor electrical properties, with potential advantages for large area deposition and low cost/kA {center_dot} m of wire.

Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growth and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis.

Chemical microsensors rely on partitioning of airborne chemicals into films to collect and measure trace quantities of hazardous vapors. Polymer sensor coatings used today are typically slow to respond and difficult to apply reproducibly. The objective of this project was to produce a durable sensor coating material based on graphitic nanoporous-carbon (NPC), a new material first studied at Sandia, for collection and detection of volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical warfare agents (CWA) and nuclear processing precursors (NPP). Preliminary studies using NPC films on exploratory surface-acoustic-wave (SAW) devices and as a {micro}ChemLab membrane preconcentrator suggested that NPC may outperform existing, irreproducible coatings for SAW sensor and {micro}ChemLab preconcentrator applications. Success of this project will provide a strategic advantage to the development of a robust, manufacturable, highly-sensitive chemical microsensor for public health, industrial, and national security needs. We use pulsed-laser deposition to grow NPC films at room-temperature with negligible residual stress, and hence, can be deposited onto nearly any substrate material to any thickness. Controlled deposition yields reproducible NPC density, morphology, and porosity, without any discernable variation in surface chemistry. NPC coatings > 20 {micro}m thick with density < 5% that of graphite have been demonstrated. NPC can be 'doped' with nearly any metal during growth to provide further enhancements in analyte detection and selectivity. Optimized NPC-coated SAW devices were compared directly to commonly-used polymer coated SAWs for sensitivity to a variety of VOC, TIC, CWA and NPP. In every analyte, NPC outperforms each polymer coating by multiple orders-of-magnitude in detection sensitivity, with improvements ranging from 103 to 108 times greater detection sensitivity! NPC-coated SAW sensors appear capable of detecting most analytes tested to concentrations below parts-per-billion. In addition, the graphitic nature of NPC enables thermal stability > 600 C, several hundred degrees higher than the polymers. This superior thermal stability will enable higher-Temperature preconcentrator operation, as well as greatly prolonged device reliability, since polymers tend to degrade with time and repeated thermal cycling.

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The superconducting and structural properties of YBa2Cu 3O7-δ (YBCO) films grown from chemical solution deposited (CSD) metallofluoride-based precursors improve by using high heating rates to the desired growth temperature. This is due to avoiding the nucleation of undesirable a-axis grains at lower temperatures, from 650 to 800 °C in p(O2) = 0.1%. Minimizing time spent in this range during the temperature ramp of the ex situ growth process depresses a-axis grain growth in favor of the desired c-axis orientation. Using optimized conditions, this results in high-quality YBCO films on LaAlO3(100) with J c(77 K)∼3 MA/cm2 for films thicknesses ranging from 60 to 140 nm. In particular, there is a dramatic decrease in a-axis grains in coated-conductors grown on CSD Nb-doped SrTiO3(100) buffered Ni(100) tapes. © 2003 Elsevier B.V. All rights reserved.

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